Sean Mason

Investigating chemical constraints to the measurement of phosphorus in soils using diffusive gradients in thin films (DGT) and resin methods

The effect of potential chemical constraints on the performance of two relatively new soil P testing methods, anion exchange membrane (AEM) and diffusive gradients in thin films (DGT), were evaluated. Exposures to ranges of anion (Cl(-), NO(3)(-), SO(4)(2-) and HCO(3)(-)) concentrations relevant to agricultural soils had minimal effect on P recoveries using DGT. It has also been shown previously that DGT P recoveries are unaffected by varying pH (3-9). In contrast, increasing NO(3)(-) and SO(4)(2-) concentrations in solution reduced the recovery of P using the resin method (anion exchange membrane, AEM) by 24% at 50mgL(-1) NO(3)(-) and by 47% at 12mgL(-1) SO(4)(2-) when the P concentration of the test solution was 2mgL(-1). Phosphorus sorption by the resin decreased with increasing Cl(-) concentrations until there was a 100% decrease at 300mgL(-1) Cl(-) when the P concentration of the test solution was 2mgL(-1) and a 92% reduction at 700mgL(-1) Cl(-) when the P concentration of the test solution was 0.2mgL(-1). There was also a small but significant effect of carbonate species on P sorption to the resin at carbonate concentrations that can occur in agricultural soils. Changing the pH of the solution had minimal effects on the resin P measurements in solutions above pH 4, but below pH 4, resin P measurements decreased dramatically. A poor coefficient of determination for the regression fit between DGT and resin measurements on eight agricultural soils suggested that these two methods are measuring different amounts of P for different soils. Resin P measurements increased significantly, but non-uniformly across soils, when the soil:water ratio was decreased but this did not result in an improved relationship with DGT P. There was a minimal effect on measured P using either Cl(-) or HCO(3)(-) as counter ions on the resin.

Soil phosphorus tests I: What soil phosphorus pools and processes do they measure?

Abstract. The phosphorus (P) status of 535 surface soils from all states of Australia was assessed using the following soil P tests: Colwell-P (0.5 m NaHCO3), Olsen-P (0.5 m NaHCO3), BSES-P (0.005 m H2SO4), and Mehlich 3-P (0.2 m CH3COOH + 0.25 m NH4NO3 + 0.015 m NH4F + 0.013 m HNO3 + 0.001 m EDTA). Results were correlated with soil P assays selected to estimate the following: soil solution P concentration (i.e. 0.01 m CaCl2 extractable P; Colwell-P/P buffer index); rate of P supply to the soil solution (i.e. P released to FeO-impregnated filter paper); sorbed P (i.e. Colwell-P); mineral P (i.e. fertiliser reaction products and/or soil P minerals estimated as BSES-P minus Colwell-P); the diffusive supply of P (i.e. P diffusing through a thin gel film, DGT-P); and P buffer capacity (i.e. single-point P buffer index corrected for Colwell-P, PBICol). Across all soils, Colwell-P and BSES-P were highly correlated with FeO-P (r = 0.76 and 0.58, respectively). Colwell-P was moderately correlated with mineral P (r = 0.24), but not solution P. Olsen-P and Mehlich-P were both highly correlated with FeO-P (r = 0.80 and 0.78, respectively) but, in contrast to Colwell-P and BSES-P, also showed moderate correlations with soil solution P (r = 0.29 and 0.34, respectively) and diffusive P supply (r = 0.31 and 0.49, respectively). Correlation coefficients with mineral P were r = 0.29 for Olsen-P and r = 0.17 for Mehlich-P. Soils were categorised according to their pH, clay activity ratio, content of mineral P and CaCO3 content, and the relationships between the empirical soil P tests examined for each soil category. Olsen-P and Colwell-P were correlated across all soil categories (r range 0.66–0.90), and a widely applicable linear equation was obtained for converting one soil test to the other. However, the correlations between other soil tests varied markedly between soil categories and it was not possible to develop such widely applicable conversion equations. Multiple step-up linear regressions were used to identify the key soil properties affecting soil solution P, P buffer capacity, and diffusive P supply, respectively. For all soil categories, solution P concentration (measured by CaCl2-P) increased as rate of P supply (measured as FeO-P) increased and P buffer capacity decreased. As an assay of sorbed P, Colwell-P alone did not significantly (P > 0.05) explain any of the variability in soil solution P, but when used in the index (Colwell-P/P buffer index), it was highly correlated (r = 0.74) with CaCl2-P. Soil P buffer capacity was dependent on different properties in different soil categories, with 45–65% of the variation in PBI accounted for by various combinations of Mehlich-Al, Mehlich-Fe, total organic C, clay content, clay activity ratio, and CaCO3 content, depending on soil category. The diffusive supply of P was primarily determined by rate of P supply (measured as FeO-P; r range 0.34–0.49), with significant (P < 0.05) small improvements due to the inclusion of PBICol and/or clay content, depending on soil category. For these surface soil samples, key properties of pH, clay activity ratio, clay content, and P buffer capacity varied so widely within individual Australian Soil Orders that soil classification was not useful for inferring intrinsic surface soil P properties such as P buffer capacity or the relationships between soil P tests.

Soil phosphorus tests II: A comparison of soil test–crop response relationships for different soil tests and wheat

Abstract. The performance of a wide range of soil phosphorus (P) testing methods that included established (Colwell-P, Olsen-P, BSES-P, and CaCl2-P) and more recently introduced methods (DGT-P and Mehlich 3-P) was evaluated on 164 archived soil samples corresponding to P fertiliser response experiments with wheat (Triticum aestivum) conducted in south-eastern Australia between 1968 and 2008. Soil test calibration relationships were developed for relative grain yield v. soil test using (i) all soils, (ii) Calcarosols, and (iii) all ‘soils other than Calcarosols’. Colwell-P and DGT-P calibration relationships were also derived for Calcarosols and Vertosols containing measureable CaCO3. The effect of soil P buffer capacity (measured as the single-point P buffer index corrected for Colwell-P, PBICol) on critical Colwell-P values was assessed by segregating field sites based on their PBICol class: very very low (15–35), very low (36–70), low (71–140), and moderate (141–280). All soil P tests, except Mehlich 3-P, showed moderate correlations with relative grain yield (R-value ≥0.43, P < 0.001) and DGT-P exhibited the largest R-value (0.55). Where soil test calibrations were derived for Calcarosols, Colwell-P had the smallest R-value (0.36), whereas DGT-P had an R-value of 0.66. For ‘soils other than Calcarosols’, R-values >0.45 decreased in the order: DGT-P (r = 0.55), Colwell-P (r = 0.49), CaCl2-P (r = 0.48), and BSES-P (r = 0.46). These results support the potential of DGT-P as a predictive soil P test, but indicate that Mehlich 3-P has little predictive use in these soils. Colwell-P had tighter critical confidence intervals than any other soil test for all calibrations except for soils classified as Calcarosols. Critical Colwell-P values, and confidence intervals, for the very very low, very low, and low P buffer capacity categories were within the range of other published data that indicate critical Colwell-P value increases as PBICol increases. Colwell-P is the current benchmark soil P test used in Australia and for the field trials in this study. With the exception of Calcarosols, no alternative soil P testing method was shown to provide a statistically superior prediction of response by wheat. Although having slightly lower R-values (i.e. <0.1 difference) for some calibration relationships, Colwell-P yielded tighter confidence intervals than did any of the other soil tests. The apparent advantage of DGT-P over Colwell-P on soils classified as Calcarosols was not due to the effects of calcium carbonate content of the analysed surface soils.

Relationship between phosphorus concentration in surface runoff and a novel soil phosphorus test procedure (DGT) under simulated rainfall

There is a need to be able to identify soils with the potential to generate high concentrations of phosphorus (P) in runoff, and a need to predict these concentrations for modelling and risk-assessment purposes. Attempts to use agronomic soil tests such as Colwell P for such purposes have met with limited success. In this research, we examined the relationships between a novel soil P test (diffuse gradients in thin films, DGT), Colwell P, P buffering index (PBI), and runoff P concentrations. Soils were collected from six sites with a diverse range of soil P buffering properties, incubated for 9 months with a wide range of P additions, and then subjected to rainfall simulation in repacked trays growing pasture. For all soil and P treatment combinations, the relationship between DGT (0–10 mm) and runoff P was highly significant (P < 0.001, r2 = 0.84). Although there were significant curvilinear relationships between Colwell P and runoff P for individual soils, there were large differences in these relationships between soils. However, the inclusion of a P buffering measure (PBI) as an explanatory variable resulted in a highly significant model (P < 0.001, R2 = 0.82) that explained between-soil variability. We conclude that either DGT, or Colwell P and PBI, can be used to provide a relative measure of runoff P concentration.

Optimization of the diffusive gradients in thin films (DGT) method for simultaneous assay of potassium and plant-available phosphorus in soils

Potassium (K) and phosphorus (P) are two important macronutrients for crops, and are usually applied to soils as granular fertilizer before seeding. Therefore, accurate soil tests prior to planting to predict crop response to fertilizers are important in optimizing crop yields. Traditional methods used for testing both available K and P in soils, which are based on chemical extraction procedures, are to be soil-type dependent, and the predictive relationships across a broad range of soils are generally poor. The diffusive gradients in thin films (DGT) technique, based on diffusion theory, is extensively used to measure the diffusive supply of trace elements, metals and some nutrients in soils and water. When DGT is used to assess plant-available P in soils, a good relationship is found between crop response to P fertilizer and concentrations of P in soil measured by DGT, and therefore the DGT method provides a more precise recommendation of P fertilizer requirements. Adaptation of the DGT method to measure plant-available K in soils has already been attempted [1], but limitations were reported due to the non-uniform size of the resin gel, decreased K binding rate of the gel at long deployment times and a limited ability to measure a wide range of K concentrations. To eliminate these problems, a new resin gel has been developed by combining Amberlite and ferrihydrite. This mixed Amberlite and ferrihydrite (MAF) gel has improved properties in terms of handling and even distribution of Amberlite in the gel. The elution efficiencies of the MAF gel for K and P were 90% and 96%, respectively. The diffusion coefficient of K through the diffusive gel was 1.30 × 10(-5)cm(2)s(-1) at 22 ± 1°C and was stable through time. Since ferrihydrite is already used in DGT P testing, the ability of the MAF gel to assess available P simultaneously was also assessed. The MAF gel performed the same as the traditional ferrihydrite gel for available P assessment in a wide variety of agricultural soils. This means that the newly developed gel has the potential to measure K and plant-available P in soils simultaneously.

Use of handheld mid-infrared spectroscopy and partial least-squares regression for the prediction of the phosphorus buffering index in Australian soils

The development of techniques for the rapid, inexpensive and accurate determination of the phosphorus (P) buffer index (PBI) in soils is important in terms of increasing the efficiency of P application for optimum crop requirements and preventing environmental pollution due to excessive use of P fertilisers. This paper describes the successful implementation of partial least-squares regression (PLSR) from spectra obtained with bench-top and handheld mid-infrared (MIR) spectrometers for the prediction of PBI on 601 representative Australian agricultural soils. By contrast, poor predictions were obtained for available (Colwell) P. Regression models were successfully derived for PBI ranges of 0–800 and 0–150, the latter range resulting in the optimum model considering the dominance of low PBI soils in the sample set. Concentrations of some major soil minerals (mainly kaolinite and gibbsite content for high PBI, and smectites or illites for low PBI), quartz (representative of low surface area of soils) and, to a lesser extent, carbonate and soil organic matter were identified as the main drivers of the PBI models. Models developed with soils sieved to <2 mm presented an accuracy similar to those developed using fine-ground material. The accuracy of the PLSR for the prediction of PBI by using bench-top and handheld instruments was also similar. Our results confirm the possibility of using MIR spectroscopy for the onsite prediction of PBI.

Application of the diffusive gradients in thin films technique for available potassium measurement in agricultural soils: Effects of competing cations on potassium uptake by the resin gel

The utilization of Amberlite (IRP-69 ion-exchange resin, 100-500 wet mesh) as the binding phase in the diffusive gradients in thin films (DGT) technique has shown potential to improve the assessment of plant-available K in soils. The binding phase has recently been optimized by using a mixed Amberlite and ferrihydrite (MAF) gel which results in linear K uptake over extended deployment periods and in solutions with higher K concentrations. As restriction of K uptake by Ca on the Amberlite based resin gel has been previously proposed, potential competing effects of Ca(2+), Mg(2+) and NH(4+) on K uptake by the MAF gel were investigated. These cations had no effect on K elution efficiency which was 85%. However, K uptake by the MAF gel was restricted in the presence of competing cations in solution. Consequently, the diffusion coefficient of K decreased in the presence of cations compared to previous studies but was stable at 1.12×10(-5)cm(2)s(-1) at 25°C regardless of cation concentrations. Uptake of K by the DGT device was affected by the presence of excessive Ca in more than 30% of twenty typical Australian agricultural soils. However, this problem could be circumvented by using a shorter deployment time than the normal 24 h. Moderate correlation of concentrations of K extracted by DGT with Colwell K (extracted by NaHCO(3), R(2)=0.69) and NH4OAc K (R(2)=0.61) indicates that DGT measures a different pool of K in soils than that measured by the standard extractants used. In addition, the MAF gel has the ability to measure Ca and Mg simultaneously.

Phosphorus and nitrogen fertiliser use efficiency of wheat seedlings grown in soils from contrasting tillage systems.

AimsThis paper assessed the effect that the vertical stratification of nutrients in conservation cropping systems of Australia has on phosphorus (P) and nitrogen (N) fertiliser use efficiency.MethodsIntact soil cores from two long-term tillage experiments, located on a Vertosol and on a Calcarosol were used to assess if tillage system (zero tillage - ZT vs conventional tillage - CT) and soil water influence fertiliser use efficiency (using 33P and 15 N) of wheat under controlled growth conditions.ResultsAdding P increased shoot growth and P uptake on the Calcarosol, provided the surface remained moist and N was applied. The percentage of plant P derived from fertiliser (Pdff) was greater on the Calcarosol regardless of tillage practice. Pdff increased when the soil remained wet or when N was added. The percentage of N derived from fertiliser (%Ndff) was not affected by tillage practice on the Vertosol but when the soil surface was allowed to dry, it was significantly greater under ZT than CT on the Calcarosol. Adding P increased N fertiliser recovery but tillage practice had no effect.ConclusionThe effect of tillage practice on P and N fertiliser use efficiency depends on soil and topsoil water status.

Use of 33P to trace in situ the fate of canola below-ground phosphorus, including wheat uptake in two contrasting soils

Our understanding of the contribution of crop root residues to phosphorus (P) cycling is mainly derived from studies using excavated roots re-introduced to soil. This study aims to quantify total below-ground P (BGP) of mature canola in situ and to estimate directly the proportion accessed by subsequent wheat. 33P-Labelled phosphoric acid was fed by stem wick to canola (Brassica napus) grown in sand or loam in pots. Shoots were removed from all plants at maturity. Half of the pots were destructively sampled. After a 3-week fallow, wheat was grown for 5 weeks in the remaining undisturbed pots. At canola maturity, 23–36% of the 33P was partitioned in recovered roots and 34–40% in the soil. More 33P was recovered in the loam than the sand. Within the soil, 6–10% of the fed 33P was present in resin P and 3–5% was in hexanol-released P pools. Ratios of shoot P : BGP (8 : 1 in sand and 15 : 1 in loam) were much narrower than those of shoot P : recovered root P (17 : 1 in sand and 39 : 1 in loam). A greater proportion and amount of the mature canola BG33P was recovered by wheat grown in the loam (26%, 2.6 mg/plant) than in the sand (21%, 1.5 mg/plant). The majority of canola BG33P remained in the bulk soil. Input of P below-ground by mature canola and subsequent P benefit to wheat was greater in loam than sand. The P from canola below-ground residues contributed up to 20% of P uptake in wheat during the first 5 weeks of growth. Longer term benefits of P from below-ground residues require investigation.

Comparison of soil analytical methods for estimating wheat potassium fertilizer requirements in response to contrasting plant K demand in the glasshouse

The traditional soil potassium (K) testing methods fail to accurately predict K requirement by plants. The Diffusive Gradients in Thin-films (DGT) method is promising, but the relationship between the DGT-measured K pool and plant available K is not clear. Wheat (Triticum aestivum L., cv. Frame) was grown in 9 Australian broad acre agricultural soils in a glasshouse trial until the end of tillering growth stage (GS30) with different plant K demands generated by varying plant numbers and pot sizes. Different K concentrations in soils were varied by 4 rates of K fertilizer application. The relative dry matter and K uptake were plotted against the soil K test value (CaCl2, Colwell and NH4OAc and DGT K measurements). To obtain 90% of maximum relative dry matter at low root density (closest to field conditions), the critical value of the NH4OAc K method was 91 (R2 = 0.56) mg kg−1. The DGT K method was not able to accurately predict relative dry matter or K uptake due to a weak extraction force for K from soils with high CEC values. Further endeavor on increasing K extraction force of the DGT method is warranted to obtain accurate plant available K results.